Acid substituted hydroxy alkylr-



Reissued Aug. 13, 1940 ACID ZILI I L mm AMINES AND PROCESS OI ROXYALKYL- MAKING SAME Wolf Chicago, 111..

Ninol, Ina, (hicago, Ill. Illinois I Y alignmto a corporation of No.2,173,058, dated Sopol'llillll tember 12, 19, Seth! No. 271,711, May

1939. Serial No. 3303'" Claims.

My invention relates to a new class of chemical compouncb and to aprocess for preparing such compoimds.

The chief object of the invention is the production of new chemicalcompounds or reactirm mixtures comprising condensation productscontaining such novel chemical compounds.

I have discovered that hydroxy alkylamines or alblolamines may becondensed with higher molecular weight organic acid substances oracylating compounds such as the free acids, esters of such acids such asthe monoglycerides, or halides of such acids, or any other derivativethereof which will condense with the ivdroxy alkylamine or alkylolamineto split out water or acids so as to bring about a union of the twomolecules. In the case of tertiary hydroxy alkylamines such astriethanolamine, for example, only esters are formed. In those caseswhere a non-tertiary go alkylolamine as, by way of illustration, amonohydroxy alhlolamine, such as monoethanolamine, is condensed with ahigher fatty acid, as shown for example in Examples 1, 2 and 9, amidesand ester-amidw may and usually do form, in certain cases, inpredominating amounts.

Thus, for example, more specifically, I have found that whenmonoethanolamine or any hydroxy almlamine is condensed with a vegetalfatty acid or a higher molecular weight organic acid, preferably a fattyacid such as stearic acid, oleic acid, linoleic'acid, or a highermolecular weight fatty acid halide or monoglyceride or any ester 01'ajhigher fatty acid with a polyhydroxy 'alcohol, or higher molecularweight organic sulpho-chlorides or sulphonic acid derivatives of highermolecular weight organic compounds or any other reactive group,condensation products will form by the union of the monoethanolamine orthe like with the higher molecular weight 'organic acid or derivativethereof with the splitting out of either water or an acid. The resultingcondensation products are, in general, basic and form salts with anychemicals having acidic groups as, for example, hydrochloric acid,acetic acid and the like.

The condensation products of my invention are sharply distinguishable inchemical structure from and have many radically different propertiesthan the salts or soaps resulting from the interaction of hydroxyalkylamines with higher fatty acids or the like. In the case of theformation of the salts or soaps of the hydroxy alkylamines with higherfatty acids or the like, the two compounds combine, forming an additionproduct. on the other hand, my condensation Application for reissueApril 18, 1940,

products result from a union of the hydroxy alkylamine with the higherfatty acid or the like whereby water or an acid, as stated, splits out.

It will be seen, therefore, that in the production of the condensationproducts of my invention a reaction temperature must be employed whichis sufiicientl'y high to split out water or an acid as a result of theunion of the molecules of hydroxy alkylamine and higher molecular weightorganic acid substance or acylating compound. Where the free acid isemployed in the condensation reaction, in which case water splits out,it will be seen that a temperature of at least about degrees C. shouldbe utilized. However, for appreciable speed of reaction, it is advisableto employ more elevated temperatures and, as a general rule, atemperature range of degrem C. to degrees C. will serve in most cases.It,

will be understood, of course, that temperature. somewhat lower than thepreferred range may be employed as well as higher temperatures but in nocase, obviously, will the temperature be suiiiciently high to causedecomposition of the reacting ingredients or the resulting product. Thelength of time for carrying out the reaction will likewise vary but,within the preferred temperature operating range, a few hours willusually sufllce, excellent results being obtained in most cases bycarrying out the reaction for from two to four hours.

For the benefit of those skilled in the art, I give hereinafter a numberof representative examples which are by no means exhaustive .but which Ideem suflicient to teach those skilled in the art the manner in which myinvention may be practiced:

1. One molof monoethanolamine is condensed with one mol of stearlc acidat 150 degrees c, t 175 degrees C. for two to four hours, whilestirring.

2. One mol of monoethanolamine acetate is condensed with one mol ofstearic acid at 150 degrees C. to 175 degrees C. for two to four hours,while stirring.

3. One mol of triethanolamine is condensed with one mol of linoleic acidat 150 degrees C. to 1'75 degrees C. for two to four hours, whilestirring.

4. One mol of triethanolamine acetate is condensed with one mol oflinoleic acid at 150 degrees C. to 1'15 degrees C. for two to fourhours, while stirring.

5. One mol .of benzoyl chloride is condensed with one mol of methyldiethanolamine at 150 (worrisome. forahoutthneor whilestirring Onemolomolhftriethanolamin ati'lfidegreesc. for ourhourawhilestin'ing.

7.Cmemo1ofabieticacidiscondensedwith molofbutyldiethanolamlne at1li0degrea C. tol'liidegrees C. forthreetofour hours, while I 8.Twomolsofahighermolecmar weight fattyacldchloridesuchasstearicacidchlorideare 9.Twomolsofahighermolecuiarweightfattyacid,suchasstcarlcacid.arecondensedwithone moi-of monoethanolamine atiiiodegrees C. to 1'15 degrees C. fortwotofourhours, with stirring.

10. One mol of triethandamine is condensed.

withonemoiofuearicacidat 150de'greesC.to 175 degrees C. fortwotofourhours, withstirring. 11. One moi of palmitic acid is condensed withonemolottriethanolamineatiwdegreescto 175 degrees C. for two tofo'urhours, with stir- 12. One moi of lauric acid is condensed with'onemoioi'trlethanolamineatahout 175 degrees C. for two to four hours,with stirring.

13.0nemoiofstearicacidiscondensedwithonemoiofasecondaryhydronalkylaminesuchasdlethanolamineatlwdegreesatoi'lidegrees C.-iortwotofourhours.

14. One moi of triethanolamine is condensed with onemoloioleicaeidatabout i'lfid'egrees Gloriourhours.

-15. One mol of monoethanoiamine is condcnsed with one moi oflauric acidat about 175' degreescforfourhours. 18.0nemo1 ofmonoethanolamineiscondensedwithonemoioioleicacidatlfiildegreesqtoi'mdegreeaafortwotofourhours.

17. One moi of diethanolamine is condensed withonemoloilaurlcacidat150degreesC.to l'liidegreescJortwotoiourhoin-s.

Itisclearthatthehydroxyalkylaminuandthehigherfattyacidsorthelikemaybecondensed in varying molai proportionsThus, for example, one moi of the hydron alblamine. such as.trlethanolamine. may be condensed with one,-

twoorthreemolsothigheri'attyacidorthelike. The hydroxy aikylamines oralkylolamines whichmay be employed in the condensation reaction include.in addition to those mentioned in the various examples, primary,secondary and tertiary hydroxy alkylamines or. alkylolamines such as thepropanoiamines, butanolamines, ethanol hutanolamines, diethanolbutanolamines; alkyl derivatives of hydroxy alkylamines oralkylolamines, that is. hydro alkylamines wherein hydrogen attached tonitrogen is replaced byalkyl such as ethyl, methyl, butyl and the like;as

well as mixtures of: these and other hydronQalmaasnmuenmmm bensoylchloride, stearic acid chloride, and like. Of particular usefulness arethe molecular-weight fattyacidswhicharederifromoilsandfatsoi'animalandvegetableoriainandwhichmaybedenotedasvegetalfattyauds. It will be understood. ofcourse,that mixtures oftheseaswellasotherhiaherorsanic acidsor pounds may beemployed and that such condensed with either substantially pure hydrowalkylamines or mixtures thereof such as Wmay be found, for example, incommercial prod- The condensation products of my invention iunction.among other things, as emulsifying and dispersing agents, aspreeipitants, as wetting agents and the like. Thus, for example, theymay be employed in dispersions or emulsions containing water andwater-immiscible materials such as oils. The condensation products havevaluable properties also in the dye industry where, for example, theymay be employed to disperse vat dyestuflsinaqueousmedimaswellasfortheproduction of -modiiled dye products as disclosed in Patent No.2,022,678.

Wherever the term "condensation product is employed, it' will beimderstcod to cover a re action product between an acid or acylatingcompound and an alkylolamine wherein wateror a'ci'd orthe likeissplitoutasaresult of theunion oi the molecules of acid or acylatlng compoundand alkyloiamine: similarly, the term "condensing" is employed to coveraprocess wherein water polmd and alkylolamine. i

The term "acylating compound", as used herein, is intended tocoversuchcompmmdsas free higher fatty acids, acyl halidescthereoi andother compounds whichreactwith alkylolaminestointroduce an acyl radicalthereinto.

The present application is a continuation-inpart of my earlierapplication, Serial No. 478.235. flied August 18, 1930.

WhatIcla-imasnewanddeslreto protecthy Reissue Letters Patent of theUnited States is:

1. A chemical compound in the form of an ester comprisingtriethanolamine in which one -H of the "OE" groups is substituted by ahither organic acid substances or acylating com- I.acidortheiikeissplitoutasa'resultofthe.unionofthemoleculesofacidoracylating com- 6. An ester-amide ofahydrm-alkyl amine and a higher aliphatic acyiating compoimd.

'1. An ester-amide oi a-hydroxy-alkyi amine and a vegetal fatty acid. 8.A neutralized ester-amide of a hydroxyaliwl amine andahigherfattyacid.

9.Theprocess for the manufacture ofdis- 10. The process for themanufacture of dispersing agents which comprises condensing atrihydroxy-alkyl amine with a higher aliphatic acylating compound.

11. Dispersing agents comprising a condensation product of adi-hydroxy-alkyl amine and a higher aliphatic acylating compound.

12. Dispersing agents comprising an ester of a tri-hydroxy-alkyl aminewith a higher aliphatic acylating compound.

13. Dispersing agents comprising a condensation product of ahydroxy-ethyl amine and a higher fatty acylating compound.

14. An ester of an aliphatic hydroxy-ethyl mono-amine with a vegetalfatty acid.

15. An ester of a tri-hydron-ethyl amine with a vegetal fatty acid.

16. Condensation products of higher fatty acids with a member selectedfrom the group consisting of mono-ethanolamine, diethanolamine,triethanolamine and mixtures thereof.

17. Dispersing agents comprising an amide of an alkylolamine containinga primary hydroxy group and a higher aliphatic acylating compound.

18. The process for the manufacture of dispersing agents which comprisescondensing a higher fatty acylating compound with a hydroiwalkyl aminecontaining hydrogen directly attached to nitrogen and containing aprimary hydroxy group.

19. The process for the manufacture of dispersing agents which comprisescondensing a hydroxy-alkyl amine containing hydrogen directly attachedto nitrogen and a primary hydroxy group with a higher aliphaticacylating compound in a quantity insufficient for saturating bothhvdroxy and amino groups present in the molecule of the hydroxy-alkylamine emp oyed- 20. The process for the manufacture of dispersing agentswhich comprises condensing a hydroxy-alkyl amine containing hydrogendirectly attached to nitrogen with a higher aliphatic acylating compoundin a quantity suiiicient i'or saturating hydroxyl and amino groupspresent in the molecule of the hydroxy-alkyl amine employed.

21. An ester of a hydroxy-alkyl amine having at least two hydroxy groupsand a higher aliphatic acylating compoimd.

22. A neutralized ester of a hydroxy-alkyl amine having at least twohydroxy groups and a higher aliphatic acylating compound.

23. Dispersing agents comprising an ester of a hydroxy-alkyl aminehaving at least two hydroxy groups and a higher fatty acid.

24. Condensation products of higher fatty acids with alnlolaminescontaining hydrogen directly connected to nitrogen and at least oneprimary hydroxy group.

25. Condensation products of higher aliphatic acids andalkylolamines-containing at least one Cal-140K group and whereinhydrogen directly attached to the nitrogen otthe alkylolamines isreplaced by aikyl.

. Condensation products of higher aliphatic acids and alkylolaminescontaining at least one CaHsOHI group and wherein hydrogen directlyattached to the nitrogen of the alkylolamines is replaced by methyl. I

27. Condensation products of higher fatty acids and alkylolaminescontaining at least one CzH'AOH group and wherein hydrogen directlyattached to the nitrogen of the alkylolamines is replaced by alhl.

28. Condensation products of higher fatty acids and alkylolaminescontaining at least one Cal-140E group and wherein hydrogen directlyattached to the nitrogen of the alkylolamines is replaced by methyl.

29. The process for the manufacture of dispersing agents which comprisescondensing a higher aliphatic acylating compound with a hydroxy-alkylamine containing both a primary amino and a primary hydroxy group.

30. A condensation product of a higher aliphatic acylating compound witha hydroxyalkyl amine containing hydrogen directly attached to nitrogenand a primary hydroxy group.

31. Dispersing agents comprising higher fatty acid amides ofmonoethanolamine.

32. Condensation products in accordance with claim 31 wherein the higherfatty acid is a member selected from the group consisting of stearicacid, oleic acid, and lauric acid.

33. Condensation products of diethanolamine with a higher fatty acidselected from the group consisting of stearic acid, oleic acid, andlauric acid.

34. Condensation products of higher fatty acids and hydroxy-alkyl aminescontaining at least one ChHrOH group.

35. Condensation products of alkylolamines having at least two hydroxygroups with higher fatty acids.

36. Condensation products of alkylolamines containing hydrogen directlyattached to nitrogen with higher fatty aclds selected from the groupconsisting of stearic acid, oleic acid, and lauric acid. Y

37. Condensation products in accordance with claim 35 wherein the higherfatty acids are selected from the group consisting of stearic acid,oleic acid, and lauric acid.

38. Condensation products of higher molecular weight aliphatic acylatingcompounds with alkylolamines containing a primary hydroxy group andwherein said primary hydroxy group of the alkylolamines is directlyattached to a carbon atom other than a carbon atom to which nitrogen ofthe alkylolamines is directly attached and wherein alkyl is directlyattached to nitrogen of theallgvlolamines.

39. Condensation products of higher molecular weight fatty acidacylating compounds with ethanolamines containing a primary hydroxygroup and wherein said primary hydroxy group of the ethanolamines isdirectly attached to a carbon atom other than a carbon atom to whichnitrogen of the ethanolamines is directly attached and wherein methyl isdirectly attached to nitrogen of the ethanolamines.

40. A higher fatty acid amide of a hydroflallgvl amine containing aprimary hydrcxy group.

